Synthesis and Cycloaddition Reactions of 1-Azido-1,1,2,2-tetrafluoroethane.

A new fluorinated azidoethane─1-azido-1,1,2,2-tetrafluoroethane─was prepared in quantitative yield by the addition of an azide anion to tetrafluoroethylene in a protic medium. The title azide was shown to be thermally stable and insensitive to impact. Copper(I)-catalyzed [3 + 2] cycloaddition with alkynes afforded 4-substituted N-tetrafluoroethyl-1,2,3-triazoles which underwent rhodium(II)-catalyzed transannulation with nitriles to novel N-tetrafluoroethylimidazoles or the reaction with triflic acid to enamido triflates. [3 + 2] Cycloaddition of the title azide with primary amines afforded novel 5-difluoromethyl tetrazoles.

Orientation and dynamics of water molecules in beryl.

Behavior of individual molecules of normal and heavy water in beryl single crystals was studied by 1H and 2H nuclear magnetic resonance spectroscopy. From temperature dependences of the spectra, we deduce that type-I water molecules embedded in the beryl voids are oriented quite differently from the view established in the literature: Different from the earlier assumptions, their H-H lines deviate by about 18° from the hexagonal axis. We suggest that this is due to the molecules attaching to the oxygen atoms forming the beryl structural voids by a hydrogen bond. Our analysis shows that the molecules perform two types of movement: (i) rapid librations around the axis of the hydrogen bond and (ii) less frequent orientational jumps among the 12 possible binding sites in the beryl voids. The frequencies of the librational motions are evaluated from a simple thermodynamic model, providing good quantitative agreement with the frequencies of librations from optical experiments reported earlier.

Language and ethnobiological skills decline precipitously in Papua New Guinea, the world's most linguistically diverse nation.

Papua New Guinea is home to >10% of the world's languages and rich and varied biocultural knowledge, but the future of this diversity remains unclear. We measured language skills of 6,190 students speaking 392 languages (5.5% of the global total) and modeled their future trends using individual-level variables characterizing family language use, socioeconomic conditions, students' skills, and language traits. This approach showed that only 58% of the students, compared to 91% of their parents, were fluent in indigenous languages, while the trends in key drivers of language skills (language use at home, proportion of mixed-language families, urbanization, students' traditional skills) predicted accelerating decline of fluency to an estimated 26% in the next generation of students. Ethnobiological knowledge declined in close parallel with language skills. Varied medicinal plant uses known to the students speaking indigenous languages are replaced by a few, mostly nonnative species for the students speaking English or Tok Pisin, the national lingua franca. Most (88%) students want to teach indigenous language to their children. While crucial for keeping languages alive, this intention faces powerful external pressures as key factors (education, cash economy, road networks, and urbanization) associated with language attrition are valued in contemporary society.